Process for converting granular starch to dextrose

ABSTRACT

A process for converting granular starch to a soluble hydrolysate wherein the unconverted starch retains its granular nature. The conversion is accomplished by means of a combination of a bacterial alpha-amylase and a glucoamylase at a temperature above the normal initial gelatinization temperature of the starch.

United States Patent [191 Leach et a1.

[451 Nov. 25, 1975 PROCESS FOR CONVERTING GRANULAR STARCI-I TO DEXTROSE Inventors: Harry Woods Leach, Willowbrook;

Ronald Emil Hebeda, Woodridge; Dennis John Holik, Naperville, all of Ill.

CPC International lnc., Englewood Cliffs, NJ.

Filed: Jan. 28, 1974 Appl. No.: 437,101

Related US. Application Data Continuation-in-part of Ser. No. 349,899, April 10, 1973, abandoned.

Assignee:

US. Cl. 195/31 R; 195/11 Int. Cl. C12D 13/02 Field of Search 195/31R,11, 7, 63, 114,

References Cited UNITED STATES PATENTS 1/1952 Wallerstein 195/11 6/1962 Lenny et al 195/11 3/1973 Fisher 195/31 R 3,784,476 1/1974 VanKampen et al. 195/63 FOREIGN PATENTS OR APPLICATIONS 2,025,748 12/1970 Germany 195/65 OTHER PUBLICATIONS Primary ExaminerA. Louis Monacell Assistant ExaminerThomas G. Wiseman Attorney, Agent, or FirmAlbert P. Halluin [57] ABSTRACT A process for converting granular starch to a soluble hydrolysate wherein the unconverted starch retains its granular nature. The conversion is accomplished by means of a combination of a bacterial alpha-amylase and a glucoamylase at a temperature above the normal initial gelatiniz'ation temperature of the starch.

23 Claims, No Drawings PROCESS FOR CONVERTING GRANULAR STARCH T DEXTROSE This application is a continuation-in-part of application Ser. No. 349,899, filed Apr. 10, 1973, now abandoned.

The invention of this application relates to the solubilization of granular starch by enzymes, and more particularly to the conversion of granular starch to hydrolytic products.

BACKGROUND OF THE INVENTION Starch is a polymeric carbohydrate material of very high molecular weight. Its monomeric units, termed anhydroglucose units, are derived from dextrose, and the complete hydrolysis of starch yields dextrose. In the United States, dextrose is manufactured from corn starch; in Europe from corn starch and potato starch; and in Japan from corn starch and white sweet potato starch.

Until 1960, dextrose was prepared from starch by acid hydrolysis. The method of preparation involved heating starch with hydrochloric or sulfuric acid at temperatures of 120-145C, then neutralizing the hydrolysis mixture with sodium carbonate, clarifying, and crystallizing the dextrose. Unfortunately, the yield of dextrose is lowered by the formation of relatively large amounts of reversion products, i.e., products which are formed by the recombination of dextrose molecules. Also, because of the high temperature and low pH of the hydrolysis reaction, some of the starch is converted to hydroxymethyl furfural, levulinic acid and color bodies. The formation of such degradation products is irreversible and, to the extent they are formed, the yield of desired dextrose is of course adversely affected. Still further, the use of hydrochloric acid or in some instances, sulfuric acid, and the subsequent neutralization of this acid with alkali results in the formation of inorganic salts which interfere with crystallization of the final dextrose product.

Later, hydrolysis of starch to dextrose was accomplished by means of enzymes. The principal enzyme used for such purpose was, and continues to be, glucoamylase. This enzyme effectively hydrolyzes the starch by cleaving one molecule of dextrose at a time from the starch molecule. As a practical matter, however, it is necessary first to thin the starch before subjecting it to the action of glucoamylase. This thinning step may be accomplished either by means of acid or enzyme. The starch is thinned to a D.E. of about -20, then treated with glucoamylase. This two-stage process is referred to as an acid-enzyme process or an enzyme-enzyme process, depending upon the nature of the thinning step employed. 7

In the case of the acid-enzyme process, the initial acid-thinning step also requires a rather high temperature, i.e., in the order of 120C. This of course produces starch fragments that readily retrograde, and also produces reversion products. As expected, these occur at the expense of the desired formation of dextrose.

The same is characteristic of the enzyme-enzyme process which also requires a relatively high temperature for the thinning step, viz., 85-95C. Furthermore, it is usual practice to heat the thinned starch at still higher temperatures, viz., of the order of 120-160C, to complete gelatinization of the starch and to improve filtration. In addition, certain fat-amylose complexes 2 are formed which are quite insoluble and cause filtration difficulties.

None of these processes is entirely free of processing difficulties because of the inevitable presence of retrogradation products, starch-fat complexes and reversion products. To the extent that these are formed, processing difficulties are encountered particularly in the filtration of the product mixture, and the yield of dextrose is diminished.

Wallerstein et a1. (U.S. Pat. No. 2,583,451) disclose an enzymatic hydrolysis process which does not utilize a high temperature, gelatinization step, but the yields of dextrose are quite low. Leach et al., Cereal Chemistry, Vol. 38, No. 1, January, 1961, pp. 34-46, likewise show the enzymatic hydrolysis of granular starch, with various alpha-amylases, but at low temperatures.

It is accordingly a principal object of the present invention to provide an improved process for the conversion of starch to dextrose.

It is another object of the present invention to provide a process for the solubilization of granular starch.

It is another object of the present invention to provide such a process which results in high yields of dextrose.

It is another object of the present invention to provide such a process which is characterized by the substantial absence of the above processing difficulties.

It is another object of the present invention to provide such a process which is characterized also by relatively low temperatures.

It is yet another object of the present invention to provide such a process which can be carried out conveniently and economically in one step.

SUMMARY OF THE INVENTION These and other objects are accomplished by a process for solubilizing starch comprising mixing a granular starch with water, a bacterial alpha-amylase and glucoamylase, at a temperature between the normal initial gelatinization temperature and the actual gelatinization temperature of the starch, and at a pH of from about 5.0 to about 7.0. Such process accomplishes the above objectives largely because of the combined action of the bacterial alpha-amylase and glucoamylase which results in increased solubilization of the starch, as well as increased yields of dextrose. Alternatively, these objects may be accomplished by the action of bacterial alpha-amylase alone, i.e., in the absence of glucoamylase. That is, granular starch, water and a bacterial alpha-amylase are mixed under the above conditions, to produce a soluble starch hydrolysate.

The starch may be any of those commonly available, including corn starch, waxy maize starch, tapioca starch, potato starch, white sweet potato starch, wheat starch, sago starch, sorghum starch, high amylose starch and the like. Waxy and the non-waxy starches are suitable. As indicated, the starch is granular. Corn grits and other raw materials high in starch content may be used satisfactorily.

An important advantage of the process is that it may be carried out in an aqueous slurry at relatively high concentrations. The solids content of the starch slurry is generally within the range of from about 5% to about 40% although ordinarily the solids content will be 10-30%. Lesser concentrations can of course be used, and in general as the concentration is decreased, so is the extent of starch solubilization increased, and thus the yield of dextrose is increased. As a practical matter,

iowever, it is highly desirable in most instances to use .maller volumes, i.e., higher concentrations of starch. ["his avoids or at least diminishes the considerable ex- )ense of concentrating the conversion mixture prior to :rystallization. In some cases, however, the advantage )f the present invention may be sufficient to outweigh his disadvantage, and a concentration of about :olids would be preferred.

The process herein permits the solubilization of virtuilly all of the starch in a aqueous slurry, within a )eriod of 24 hours. Furthermore, at higher concentrazions any undissolved starch can be recycled so as to mprove the overall efficiency; i.e., to solubilize more :han 90% of the starch.

The bacterial alpha-amylase preferably is one which .s active within the pH range of from about 4.0 to about 7.0 and which possesses appreciable activity at relatively low temperatures, i.e., below the temperature at which a particular starch gelatinizes. Preferred sources of such alpha-amylases include certain species of the Bacillus microorganism, viz., B. subtilis, B. licheniformis, B. coagulans and B. amyloliquefaciens. Suitable alpha-amylases are described in Austrian Pat. No. 4836/70 and in U.S. Pat. No. 3,697,378. Especially suitable amylases are those derived from B. licheniformis as described in the above Austrian patent application. Particularly preferred is that alpha-amylase derived from B. licheniformis strain NClB 8061; other specific microorganisms include B. licheniformis strains TABLE l-continued Enzyme Preparation Company Form Activity Novo B. subtilis Novo Liquid 1,599 U/ml Kleistase GM-l6 Daiwa Kasai Powder 26,593 U/g Kleistase L-l Daiwa Kasai Liquid 1,918 U/ml Rapidase SP-250 Societe Rapidase France Powder 1 1,655 U/g about 1.0 to about 10 units per gram of starch (dry ba- NCIB 8059, ATCC 6598, ATCC 6634, ATCC 8480,

ATCC 9945A and ATCC 11945. They are unusually effective in the liquefaction of granular starch, i.e., when used in the substantial absence of glucoamylase. One such enzyme is identified by the trade name Thermamyl, available from Novo Enzyme Corporation, Mamaroneck, New York. For such use the alphaamylase should be used in a concentration ranging from about 0.1 to about 25 units per gram of starch (dry basis) under conditions of pH and temperature set out earlier herein. Thermamyl is characterized by the following properties:

a. it is thermally stable; b. it is active throughout a wide range of pH; and 0. its activity and heat stability are less dependent than other alpha-amylases on the presence of added calcium ion. Typical analyses of three different Thermamyl preparations are as follows:

Still other suitable alpha-amylases which are available include the following:

TABLE I Enzyme Preparation Company Form Activity Rhozyme 1-1-39 Rohm & Haas Powder 4,874 U/g Takamine PIT-1000 Miles Powder 3,760 U/g Tenase Miles Liquid 2,043 U/ml Dex-Lo MM' Wallerstein Liquid 1,213 U/ml Novo SP-96 Novo Powder 7,310 U/g sis).

The alpha-amylase activity of an enzyme is determined as follows:

The enzyme is allowed to react with a standard starch solution under controlled conditions. Enzyme activity is determined by the extent of starch hydrolysis, as reflected by a decrease in iodine-staining capacity, which is measured spectrophotometrically. The unit of bacterial alpha-amylase activity is the amount of enzyme required to hydrolyze 10 mg. of starch per minute under the conditions of the procedure. The method is applicable to bacterial alpha-amylases, including industrial preparations, except materials which possess significant saccharifying activity.

From 0.3 to 0.5 gram of solid sample or from 0.3 to 1.0 ml. of a liquid sample is dissolved in a sufficient quantity of 0.0025 M aqueous calcium chloride to give an enzyme solution containing approximately 0.25 unit of activity per ml.

A mixture of 10 ml. of 1% Lintner starch solution, equilibrated to 60C, and 1 ml. of the enzyme sample to be tested is mixed and held in a 60C constant temperature bath for exactly 10 minutes. A l-ml. sample is removed and added to a mixture of 1 ml. of l M aqueous hydrochloric acid and about 50 ml. of distilled water. The iodine-staining capacity of such acidified sample then is determined by adding 3.0 ml. of 0.05% aqueous iodine solution, diluting to ml. with distilled water, and mixing well. The absorbance of the solution, relative to that of distilled water, is measured at 620 nm, in a 2-cm. cell. A similar measurement is made of the standard starch solution (to which water is added instead of the enzyme solution) to provide a blank absorbance.

The enzyme activity, in units/gram or /ml. is equal to (Blank Absorbance Sample Absorbance) X Dilution Factor X 50 Blank Absorbance X 10 X 10 The glucoamylase may be any of the well-known fun gal amylase preparations, particularly those derived from members of the Aspergillus genus, the Endomyces genus or the Rhizopus genus. A particularly preferred glucoamylase is that available from the process described in US. Pat. No. 3,042,584 (Kooi et al.) whereby a fungal amylase preparation is freed of undesired transglucosidase activity by treatment in an aqueous medium with a clay material. The amount of glucoamylase to be used ranges from about 0.05 unit to about 5.0 units per gram of starch (dry basis). Preferably, on an enzyme cost/performance basis, about 0.1 to about 0.3 unit of glucoamylase per gram of starch (dry basis) is used.

Glucoamylase activity units are determined as follows:

The substrate is a 15-1 8 D.E. acid hydrolysate of corn starch dissolved in water and diluted to 4.0 grams of dry substance per 100 ml. of solution. Exactly 50 ml. of the solution is pipetted into a 100 ml. volumetric flask. To the flask is added 5.0 ml. of 1.0 molar sodium acetate-acetic acid buffer (pl-I: 4.3 The flask is placed in a water bath at 60C and after 10 minutes the proper amount of enzyme preparation is added. At exactly 120 minutes after addition of the enzyme preparation the solution is adjusted to a phenolphthalein end-point with one normal sodium hydroxide. The solution is then cooled to room temperature, and diluted to volume. A reducing sugar value, calculated as dextrose, is determined on the diluted sample and on a control with no enzyme preparation added. Glucoamylase activity is calculated as follows:

where:

A glucoamylase activity units per ml. (or per gram) of enzyme preparation.

S reducing sugars in enzyme converted sample,

grams per 100 ml.

B reducing sugars in control, grams per 100 ml.

E amount of enzyme preparation used, ml. (or

grams).

S should not exceed 1.0 grams per 100 ml.

The temperature of the reaction mixture of the process herein should as indicated be between the normal initial gelatinization temperature and the actual gelatinization temperature of the starch. Ordinarily, the temperature will be at the upper end of this range. A particular advantage of the process is the fact that high temperatures are avoided. This permits a considerable savings in the cost of supplying heat to the process and minimizes the formation of color bodies with a subsequent savings in refining costs. It is interesting to note that the process can be carried out at temperatures above the normal initial gelatinization temperature of a ,starch without noticeable gelatinization as evidenced by an increase in viscosity. Despite the fact that corn .starch, for example, is considered to have a gelatinization temperature range of 6272C, i.e., its normal" gelatinization temperature range, the process. of the present invention may be carried out with corn starch at temperatures up to about 80C without any noticeable increase in viscosity. As a matter of fact, it usually is desirable to carry out the process at these higher temperatures, because of the increased rate and extent of solubilization of starch.

When the reaction is conducted at temperatures exceeding the normal initial gelatinization temperature of the starch, it is desirable to have hydrolysis products present during the reaction. One way of accomplishing this is to add the enzyme(s) to the starch at a temperature equal to or lower than the initial gelatinization 6 temperature, and then to heat the mixture to the desired temperature.

The selection of pH depends upon the particular enzymes used in the process. Ideally, the thinning enzyme and the saccharifying enzyme would exhibit their optimum activities at the same pH, but as a practical matter this is unlikely. Glucoamylase is, of course, the saccharifying enzyme and its optimum activity is exhibited at a pH of about 4.5. Thermamyl, on the other hand, exhibits its optimum activity at a pH of 5.5-7 and is not sufficiently active at a pH below 5 to promote the desired starch solubilization. The same is true generally with respect to other alpha-amylases. Accordingly, a suitable pH for the purpose of invention herein is one falling within the range of from about 5.0 to about 7.0, i.e., where the glucoamylase and alpha-amylase each are suitably active.

A preferred embodiment of the invention involves the method of ultrafiltration. By selection of a suitable semi-permeable membrane, the enzyme and unreacted starch may be completely retained by the membrane while the dextrose product, being of lower molecular weight, passes through as it is formed. Ultrafiltration is discussed in New Separation Technique for the CPI", Chemical Engineering News, 64, No. 12 (1968).

In another preferred embodiment the starch conversion mixture contains an anionic surfactant. In certain concentrations the surfactant enhances the degree of solubilization and yield of dextrose, i.e., in concentrations ranging from about 0.01 to about 1.0%. Best results are obtained with a concentration of anionic surfactant ranging from about 0.05 to about 0.50%. Typical anionic surfactants useful herein include sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium wax-substituted napthalene sulfonate, sodium stearate, and triethanolamine alkyl sulfonates where the alkyl group is derived from alcohols produced by the reduction of tallow or coconut oil glycerides. In general, the anionic dispersants herein are water-soluble salts having an alkyl group containing from about 8 to about 20 carbon atoms, a sulfonic acid or sulfuric acid ester radical, and either sodium, potassium, ammonium, or aliphatic amine having fewer than 10 carbon atoms, as the cation.

In still another preferred embodiment the process is carried out in two stages, with respect to the pH of the starch conversion mixture. The first stage conforms to that described above, i.e., the pH is maintained at from about 5.0 to about 7.0, until at least about 1 0% of the starch has been solubilized, and preferably until the solubilization of starch begins to level off. This occurs in the usual instance after about 16 hours. The conversion mixture may be filtered at this point, if desired. The pH is adjusted down to within the range of from about 4.0 to about 5.0. Within this range the activity of the glucoamylase is greater than at higher pHs and the overall result is a somewhat increased yield of dextrose.

A particularly preferred embodiment, resulting in the formation of substantial proportions of dextrose, comprises the steps of l agitating a mixture of a granular starch, water and a bacterial alpha-amylase, at'a temperature between the normal initial gelatinization temperature of the starch and the actual gelatinization temperature of the starch and at a pH of from about 5.0 to about 7.0, to convert at least 10% of the starch to a soluble hydrolysate; and (2) adjusting the temperature to 5065C and the pH to 4.0-4.8, and adding glucoamylase to saccharify the soluble hydrolysate. Step 1 gen- 7 rally requires about 12 hours; step (2) on the other and ordinarily will require a much longer time, i.e., -om about 24 hours to about 120 hours. In some in- 8 ture of corn starch) the non-solubilized starch retains its granular nature throughout the course of the conversion.

TABLE II Run Starch Enzyme-Dose Time No. Conc. BAA GA Hrs. Temp. Sol.

l 30 2 Th" 0.25 24 65C 74.8 2 30 2 Th 0.14 24 65C 76.4 3 30 2 Th 0.25 24 70C 89.2 4 30 2 Th 0.14 24 70C 88.7 5 25 2 Th 0.14 26 75C 97.6 6 25 2 Th 0.14 50 75C 94.8 7 25 8-221" 014 26 75C 96.1 8 10 B-221 0.14 50 75C 96.4 9 25 2 Th 0.14 25 65C 80.4

10 25 2 Th 0.14 24 70C 892 11 25 2 Th 0.14 22 75C 93.2

12 3O 2 Th 0.25 48" 65C 770 "units per gram of starch "bacterial alpha-amylase glucoamylase of starch solubilized 'l'hermamyl '60- 75C for 2 hours, 75C for 24 hours 60C for 24 hours. then as in f "derived from a Bacillus :ublili: microorganism and having an activity of 3910 U/g 60C for 24 hours, 65C for 24 hours tances, it is desirable to add glucoamylase to the mixure in step (1). The amounts of alpha-amylase and glucoamylase used in step (1) are the same as specified :arlier herein for the conversion of granular starch to .oluble hydrolysate in one step.

The above additional amount of glucoamylase emiloyed in the second stage ranges from about 0.1 to about 1.0 units of activity per gram of dry starch.

The starch hydrolysis product may be worked up in .he usual manner, i.e., by concentration and crystalliza- Lion.

A typical procedure for an enzymatic hydrolysis as lescribed above is as follows:

A slurry containing 125 parts of starch (dry basis) and 350 parts of distilled water is prepared in a 1-liter ;tainless steel beaker. Calcium is added if desired (as in :he case of the use of alpha-amylases other than Thernamyl), in the form of an aqueous calcium chloride soution containing 40 mg. of calcium per milliliter, to in- :rease the total amount of calcium present in the slurry )y 100 ppm (the starch contains some calcium, and so ioes the alpha-amylase). The pH is adjusted to 5.5 by :he addition of dilute aqueous sodium hydroxide; bacterial alpha-amylase and glycoamylase are added and the total weight of the slurry adjusted to 500 parts by the addition of distilled water. The beaker is placed in a. water bath, the contents stiffed and heated to 5075C and held at that temperature for the indizated time of reaction; the pH is checked periodically and readjusted to 5.5 when necessary. The product then is filtered and the filter cake washed, dried and weighed to ascertain the portion of starch remaining unsolubilized. The following data obtained via this pro- :edure is illustrative. In each case the data is based on use ofa 25-30% aqueous slurry of granular corn starch at a pH of 5.5 and a temperature of 6575C.

When the conversions are conducted at 6575C [well above the reported initial gelatinization tempera- The solubilizing influence of alpha-amylases alone on granular starch, at the elevated temperatures of this invention is shown by the data in Table III. In each case a starch slurry containing 25 or 30% of granular starch is agitated with an alpha-amylase at 6075C, at a pH of 5.5, for about 25 hours.

units per gram of starch "36 of starch solubilized 60-75C for 2 hours, C for 24 hours As pointed out earlier herein, a particularly preferred embodiment of the invention involves the preparation of dextrose via a 2-stage process: in the first stage the granular starch is converted to a starch hydrolysate by treatment with an alpha-amylase, either alone or in combination with glucoamylase, at a temperature between the normal initial gelatinization temperature and the actual gelatinization temperature of the starch and at a pH of 5-7; then in the second stage the temperature is lowered to 5065C, the pH is lowered to 4.0-4.8 and additional glucoamylase is added. These conditions are maintained for 24l20 hours. Data obtained from such a 2-stage process, wherein the combination of alpha-amylase and glucoamylase is used in the first stage is shown in Table IV. In each case the starch slurry contains 25% starch and, in the second stage, an additional 0.14 unit of glucoamylase is added after adjusting the temperature to 60C and the pH (from 5.5 in the first stage) to 4.3.

TABLE lV-continued Run No. lst Stage 2nd Stage Dextrose 3 as in No. 7. Table ll 120 hrs. 94.9 4 as in No. 8, Table 11 96 hrs. 96.2 5 as in No. 9, Table ll hrs. 97.6 6 as in No. 10, Table ll 90.5 hrs. 98.4 7 2Th +0.14 GA at 73C for 24 hrs. 42 hrs. 96.5 8 2Th+0.l4 GA at 73C for 12 hrs. 82 hrs. 96.5 9 2Th+0.l4 GA at C for 12 hrs. 86 hrs. 96.8 l0 as in No. 11. Table ll hrs. 95.8

0.l4 GA at 60C based on solids in the filtrate Additional data obtained from similar runs wherein alpha-amylase is used alone in the first stage is set forth in Table V. In each case the starch slurry contains 30% recovering from said mixture the soluble starch hyof starch.

TABLE V Run No. lst Stage 2nd Stage Sol. Dextrose l 2 Th at 6075C 0.l4 GA at 60C 97.2 95.3

for 2 hrs., 75C for hrs; for 24 hrs.; pH, pH, 4.3 5.5

2 2 Th at 60C for 0.14 GA at 60C 96.2 95.2

24 hrs., 60-7SC for 96 hrs.; for 2 hrs., 75C pH, 4.3 for 24 hrs.; pH, 5.5

3 10 8-221 at 60- 0.14 GA at 60C 942 94.8

75C for 2 hrs.. for 120 hrs.; 75C for 24 hrs.; pH, 4.3 pH. 5.5

4 l0 B-22l at 60C 0.l4 GA at 60C 95.l 93.3

for 24 hrs., 60- for 96 hrs.; 75C for 2 hrs., pH, 4.3 75C for 24 hrs.; pH, 5.5

5 2 Kleistase at 0.l4 GA at 60C 93.2 94.8

60-75C for 2 for 96 hrs.; hrs.. 75C for pH, 4.3 24 hrs.; pH. 5.5

6 l0 Kleistase at 0.l4 GA at 60C 94.9 93.2

60-75C for 2 for 96 hrs.; hrs., 75C for pH, 4.3 24 hrs.; pH, 5.5

based on solids in the filtrate All parts and percentages herein are by weight unless otherwise expressly stated.

While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modification, and this application is intended to cover any variations, uses or adaptations of the invention following, in general,

the principals of the invention and including such departures from the present disclosure as come within known or customary practice in the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as fall within the scope of the invention.

What is claimed is:

l. A process for directly converting granular starch to a soluble starch hydrolysate containing dextrose, comprising:

agitating a mixture of granular starch, water, an alpha-amylase enzyme preparation and a glucoamylase enzyme preparation at a temperature in the range from the normal initial gelatinization temperature of the starch to the actual gelatinization temperature of the starch, at a pH of from about 4.0 to

drolysate containing dextrose, whereby any residual, non-soluble starch has substantially retained its granular, ungelatinized form.

2. The process of claim 1, wherein the starch is corn starch.

3. The process of claim 1, wherein the concentration of starch is from about 5% to about 40%, by weight.

4. The process of claim 1, wherein the concentration of the alpha-amylase is from about 0.1 unit to about 25 units of activity per gram of starch.

5. The process of claim 1, wherein the amount of glucoamylase used is such as to provide from about 0.05 to about 5.0 units of activity per gram of starch.

6. The process of claim 1, wherein the alpha-amylase is derived from a Bacillus organism.

7. The process of claim 1, wherein the glucoamylase is derived from a fungal source.

8. The process of claim 1, wherein the glucoamylase is derived from an Aspergillus niger organism.

9. The process of claim 1, wherein the glucoamylase is derived from an organism of Rhizopus genus.

10. The process of claim 1, wherein the alpha-amylase is derived from a Bacillus subtillus organism.

11. The process of claim 1, wherein the alpha-amyase is derived from a Bacillus licheniformis organism.

12. The process of claim 1, wherein the mixture of granular starch, water, alpha-amylase and glucoamyase contains from about 0.01% to about 1.0% of an anonic surfactant.

13. The process of claim 1, wherein the starch is com .tarch and the conversion is conducted at a temperaure in the range of from about 60C. to about 80C.

14. The process of claim 1, wherein the starch is com .tarch and the conversion is conducted at a temperaure of from about 60C. to about 75C.

15. The process of claim 1, wherein the residual, non- .oluble starch is recycled.

16. A process for directly converting granular starch o a soluble starch hydrolysate containing dextrose, :omprising:

agitating a mixture of granular starch, water, an alpha-amylase enzyme preparation derived from Bacillus licheniformis and a glucoamylase enzyme preparation wherein the starch is present at a concentration in the range from about to about 40% by weight of the mixture, the alpha-amylase is present in the range from about 0.1 to about 25 units of activity per gram of starch, and the glucoamylase is present in an amount such as to provide from about 0.05 to about 5.0 units of activity per gram of starch,

converting and solubilizing the granular starch in said agitated mixture at a temperature in the range from the normal initial gelatinization temperature of the starch to the actual gelatinization temperature of the starch, maintaining said conditions for a period of time to produce a soluble starch hydrolysate containing dextrose, and

recovering from said mixture the soluble starch hydrolysate containing dextrose whereby any residual non-soluble starch has substantially retained its granular, ungelatinized form.

17. The process of claim 16, wherein said starch is :orn starch and the conversion and solubilization is :onducted at a temperature in the range of from about 50C. to about 75C.

18. The process of claim 16, wherein said alpha-amylase is derived from a Bacillus licheniformis strain of the group consisting of NCIB 8061, NCIB 8059, ATCC 5598, ATCC 6634, ATCC 8480, ATCC 9545A and ATCC 11945.

12 19. A process for directly converting granular corn starch to a soluble corn starch hydrolysate containing dextrose comprising:

agitating a mixture of granular corn starch, water an alpha-amylase enzyme preparation derived from Bacillus licheniformis and a glucoamylase enzyme preparation, wherein the starch is present at a concentration in the range from about 10% to about 30% by weight of the mixture, the alpha-amylase is present in the range from about 1.0 to about 10 units of activity per gram of corn starch, and the glucoamylase is present in an amount such as to provide from about 0.05 to about 5.0 units of activity per gram of starch,

converting and solubilizing the corn starch in said agitated mixture at a temperature in the range from the normal initial gelatinization temperature to the actual gelatinization temperature of the corn starch, at a pH of from about 4.0 to about 7.0, maintaining said conditions for a period of time until at least about 90% of the corn starch is hydrolyzed to a soluble starch hydrolysate containing dextrose, and

recovering from said mixture the soluble corn starch hydrolysate containing dextrose whereby any resid ual, non-soluble starch has substantially retained its granular, ungelatinized form.

20. The process of claim 19, wherein the conversion and solubilization is conducted at a temperature in the range of from about 60C. to about C.

21. The process of claim 19, wherein an anionic surfactant is added to said agitated mixture in an amount ranging from about 0.01% to about 1.0%, by weight of the agitated mixture.

22. The process of claim 19, wherein the agitated mixture, in a first step is heated to a temperature of about 60C., and in a subsequent step heated to a temp'era'ture of about 75C. until at least about of the granular corn starch is hydrolyzed.

23. The process of claim 19, wherein the conversion and solubilization is conducted in an ultrafiltration cell wherein the enzyme preparation and non-soluble starch are retained in the cell and the soluble corn starch hydrolysate is passed through a semi-permeable membrane of said ultrafiltration cell. 

1. A PROCESS FOR DIRECTLY CONVERTING GRANULAR STARCH TO A SOLUBLE STARCH HYDROLYSSATE CONTAINING DEXTROSE COMPRISING: AGITATING A MIXTURE OF GRANULAR STARCH, WATER, AN ALPHA-AMYLASE ENZYME PREPARATION AND A GLUCOAMYLASE ENZYME PREPARATION AT A TEMPERATURE IN THE RANGE FROM THE NORMAL INITIAL GELATINIZATION TEMPERATURE OF THE STARCH TO THE ACTUAL GELATINIZATION TEMPERATURE OF THE STARCH AT A PH OF FROM ABOUT 4.0 TO ABOUT 7.0, MAINTAINING SAID CONDITIONS FOR A PERIOD OF TIME TO PRODUCE A SOLUBLE STARCH HYDROLYSTATE CONTAINING DEXTROSE, AND RECOVERING FROM SAID MIXTURE THE SOLUBLE STARCH HYDROLYSATE CONTAINING DEXTROSE, WHEREBY ANY RESIDUAL, NON-SOLUBLE STARCH HAS SUBSTANTIALLY RETAINED ITS GRANULAR, UNGELATINIZED FORM.
 2. The process of claim 1, wherein the starch is corn starch.
 3. The process of claim 1, wherein the concentration of starch is from about 5% to about 40%, by weight.
 4. The process of claim 1, wherein the concentration of the alpha-amylase is from about 0.1 unit to about 25 units of activity per gram of starch.
 5. The process of claim 1, wherein the amount of glucoamylase used is such as to provide from about 0.05 to about 5.0 units of activity per gram of starch.
 6. The process of claim 1, wherein the alpha-amylase is derived from a Bacillus organism.
 7. The process of claim 1, wherein the glucoamylase is derived from a fungal source.
 8. The process of claim 1, wherein the glucoamylase is derived from an Aspergillus niger organism.
 9. The process of claim 1, wherein the glucoamylase is derived from an organism of Rhizopus genus.
 10. The process of claim 1, wherein the alpha-amylase is derived from a Bacillus subtillus organism.
 11. The process of claim 1, wherein the alpha-amylase is derived from a Bacillus licheniformis organism.
 12. The process of claim 1, wherein the mixture of granular starch, water, alpha-amylase and glucoamylase contains from about 0.01% to about 1.0% of an anionic surfactant.
 13. The process of claim 1, wherein the starch is corn starch and the conversion is conducted at a temperature in the range of from about 60*C. to about 80*C.
 14. The process of claim 1, wherein the starch is corn starch and the conversion is conducted at a temperature of from about 60*C. to about 75*C.
 15. The process of claim 1, wherein the residual, nonsoluble starch is recycled.
 16. A PROCESS FOR DIRECTLY CONVERTING GRANULAR STARCH TO A SOLUBLE STARCH HYDROLYSATE CONTAINING DEXTROSE, COMPARISING: AGITATING A MIXTURE OF GRANULAR STARCH, WATER, AN ALPHA-AMYLASE ENZYME PREPARATION DERIVED FROM BACILLUS LICHENIFORMIS AND A GLUCOAMYLASE ENZYME PREPARATION WHEREIN THE STARCH IS PRESENT AT A CONCENTRATION IN THE RANGE FROM ABOUT 5% TO ABOUT 4% BY WEIGHT OF THE MIXTURE, THE ALPHA-AMYLASE IS PRESENT IN THE RANGE FROM ABOUT 0.1 TO ABOUT 25 UNITS OF ACTIVITY PER GRAM OF STARCH, AND THE GLUCOAMYLASE IS PRESENT IN AN AMOUNT SUCH AS TO PROVIDE FROM ABOUT 0.05 TO ABOUT 5.0 UNITS OF ACTIVITY PER GRAM OF STARCH, CONVERTING AND SOLUBILIZING THE GRANULAR STARCH IN SAID AGITATED MIXTURE AT A TEMPERATURE OF THE STARCH TO NORMAL INITIAL GELATINIZATION TEMPERATURE OF THE STARCH TO THE ACTUAL GELATINIZATION TEMPERATURE OF THE STARCH TO TAINING SAID CONDITIONS FOR A PERIOD OF TIME TO PRODUCE A SOLUBLE STARCH HYDROLYSATE CONTAINING DEXTROSE, AND RECOVERING FROM SAID MIXTURE THE SOLUBLE STARCH HYDROLYSATE CONTAINING DEXTROSE WHEREBY ANY RESIDUAL NON-SOLUBLE STARCH HAS SUBSTANTIALLY RETAINED ITS GRANULAR,, UNGELATINIZED FORM.
 17. The process of claim 16, wherein said starch is corn starch and the conversion and solubilization is conducted at a temperature in the range of from about 60*C. to about 75*C.
 18. The process of claim 16, wherein said alpha-amylase is derived from a Bacillus licheniformis strain of the group consisting of NCIB 8061, NCIB 8059, ATCC 6598, ATCC 6634, ATCC 8480, ATCC 9545A and ATCC
 11945. 19. A process for directly converting granular corn starch to a soluble corn starch hydrolysate containing dextrose comprising: agitating a mixture of granular corn starch, water an alpha-amylase enzyme preparation derived from Bacillus licheniformis and a glucoamylase enzyme preparation, wherein the starch is present at a concentration in the range from about 10% to about 30% by weight of the mixture, the alpha-amylase is present in the range from about 1.0 to about 10 units of activity per gram of corn starch, and the glucoamylase is present in an amount such as to provide from about 0.05 to about 5.0 units of activity per gram of starch, converting and solubilizing the corn starch in said agitaTed mixture at a temperature in the range from the normal initial gelatinization temperature to the actual gelatinization temperature of the corn starch, at a pH of from about 4.0 to about 7.0, maintaining said conditions for a period of time until at least about 90% of the corn starch is hydrolyzed to a soluble starch hydrolysate containing dextrose, and recovering from said mixture the soluble corn starch hydrolysate containing dextrose whereby any residual, non-soluble starch has substantially retained its granular, ungelatinized form.
 20. The process of claim 19, wherein the conversion and solubilization is conducted at a temperature in the range of from about 60*C. to about 75*C.
 21. The process of claim 19, wherein an anionic surfactant is added to said agitated mixture in an amount ranging from about 0.01% to about 1.0%, by weight of the agitated mixture.
 22. The process of claim 19, wherein the agitated mixture, in a first step is heated to a temperature of about 60*C., and in a subsequent step heated to a temperature of about 75*C. until at least about 90% of the granular corn starch is hydrolyzed.
 23. The process of claim 19, wherein the conversion and solubilization is conducted in an ultrafiltration cell wherein the enzyme preparation and non-soluble starch are retained in the cell and the soluble corn starch hydrolysate is passed through a semi-permeable membrane of said ultrafiltration cell. 